The invention includes a compositions of matter comprising a composition of the formula A+Bxe2x88x92 covalently bonded to a support, a composition comprising supported A+Bxe2x88x92 and an ionic liquid immobilized in said supported A+Bxe2x88x92 as well as a composition comprising supported A+Bxe2x88x92 having an ionic liquid immobilized in said supported A+Bxe2x88x92 and further having catalyst immobilized in the ionic liquid. Methods for making the compositions are also taught.
The art proposes AlClx based ionic liquids deposited or impregnated onto a solid. For example, EP 553,009 B1 proposes a xe2x80x9ccatalyst comprising an organic or mineral porous support and at least one mixture constituted by at least one halide of a compound chosen from Aluminum and Boron and at least one compound chosen from ammonium halides and amine hydrohalides.
U.S. Pat. No. 5,693,585 proposes a catalyst composition containing a porous organic or mineral support, preferably silica, and at least one active phase containing at least one aluminum halide, at least one quaternary ammonium halide and/or at least one amine hydrohalide, and at least one cuprous compound.
WO 99/03163 proposes the alkylation of aromatic compounds using as a catalyst a supported ionic liquid composition. The catalyst comprises an ionic liquid, which consists essentially of an organic base and a metal halide, and a support that may be a macroporous polymer or metal oxide, such as silica.
WO 00/15594 proposes a process for the carbonylation of alkyl aromatic compounds using acidic ionic liquids.
Immobilized Ionic Liquids as Lewis Acid Catalysts for the Alkylation of Aromatic Compounds with Dodecene by DeCastro et al., J. Catalysis 196, 86-94 (2000) teaches immobilized ionic liquids as Lewis Acid catalysts for the alkylation of aromatic compounds with dodecene. The ionic liquid used throughout the experiments consisted of 1-butyl-3-methylimidazolium chloride and AlCl3. The support materials that were used included SiO2, Al2O3, TiO2, ZrO2 and some mixtures of thereof.
The invention includes a composition comprising a support selected from the group consisting of organic and inorganic supports and a composition of the formula
A┐⊕Bxe2x8ax96
wherein A is selected from the group consisting of compounds of the general formulae: 
and wherein each occurrence of Z is independently selected from the formula
(Y)nXm
where
Y is OR or R
and wherein X is halide and wherein p is an integer from 1 to 4, r is an integer from 0 to 10, 1, 1xe2x80x2 and 1xe2x80x3 are integers from 0 to 4 wherein 1+1xe2x80x2+1xe2x80x3+pxe2x89xa64
n+m=3 and wherein n ranges from 0 to 3 and m ranges from 0 to 3 and wherein said cyclic systems (depicted by circles) contain 4 to 10 atom in addition to one or more nitrogen atoms, and may also contain sulfur or oxygen atoms singly or double bonded to said ring and wherein said cyclic system may be a single, double or triple ring system and wherein Bxe2x88x92 is selected from the group consisting of salts, anions, alkylates and halogenated salts of the Group Ib, IIIb, IVb, Vb, VIb, VIIb, IIIa, IVa, Va, VIa, VIIa, and VIIIa elements of the periodic table (see Basic Inorganic Chemistry, by Cotton and Wilkinson, 1976, Wiley, inside cover) and wherein g is an integer from 1 to 4, x is 1 or 2 and y is 1 or 2, wherein each R in the above formulae is independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, halogenated aralkyl, oxygen, nitrogen, or sulfur substituted alkyl, oxygen, nitrogen or sulfur substituted aryl, oxygen, nitrogen or sulfur substituted aralkyl, oxygen, nitrogen or sulfur substituted cycloalkyl groups having from 1 to 12 carbon atoms and mixtures thereof, and wherein each Rxe2x80x2 in the above formulae is independently selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, halogenated aralkyl, oxygen, nitrogen, or sulfur substituted alkyl, oxygen, nitrogen or sulfur substituted aryl, oxygen, nitrogen or sulfur substituted aralkyl, oxygen, nitrogen or sulfur substituted cycloalkyl groups having from 1 to 12 carbon atoms and mixtures thereof, and wherein said compound having the formulae A+Bxe2x88x92 is covalently bonded to said support through said A+ group.
The invention further includes a composition comprising a support selected from organic and inorganic supports having covalently bonded thereon said composition A+Bxe2x88x92 described above, wherein said composition is covalently bonded to said support through A+ and an ionic liquid coulombically attached to said support.
The invention further includes a composition comprising a support selected from organic and inorganic supports having covalently bonded thereon said composition A+Bxe2x88x92 described above, wherein said composition is covalently bonded to said support through Bxe2x88x92 and an ionic liquid coulombically attached to said support and an effective amount of a catalyst immobilized within said ionic liquid.
One skilled in the art can readily determine if the composition A+Bxe2x88x92 has been covalently bonded to the support by utilizing solid state NMR and solid state FTIR techniques to monitor the bonding.
A method of preparing a supported composition comprising;
covalently bonding a compound having the formula A+Bxe2x88x92 to a support selected from organic and inorganic supports, wherein said composition A+Bxe2x88x92 is covalently bonded to said support through A+ and wherein said composition A+Bxe2x88x92 has the formulae shown above and wherein said covalent bond is established through a chemical reaction between said support and said compound said chemical reaction being selected from the group consisting of condensation reactions, ring opening reactions, and hydrosilylation reactions which take place between said composition A+Bxe2x88x92 and said support.
The method may further comprise depositing an ionic liquid dissolved in a solvent onto said support and thereafter evaporating said solvent.
The method may still further comprise adding a catalytically active material to the composition by adding the catalytic material to said solvent along with said ionic liquid or adding a catalytic material to the composition by dissolving the catalyst in a solvent, mixing with the composition and thereafter evaporating off the solvent. The catalyst can be added prior to, following, or in conjunction with the ionic liquid.
The composition A+Bxe2x88x92 may be referred to herein as an ionic liquid moiety or a modified ionic liquid. The composition is prepared by mixing and refluxing precursors compounds which when reacted will yield the composition A+Bxe2x88x92. For example an alkylating electrophile may be refluxed with a neutral nitrogen containing compound having at least one silicon based anchor group. Such silicon based anchor groups are Si-halogen or Si-alkoxy groups or mixture thereof. Alternatively, one could reflux a neutral nitrogen containing compound having a lone electron pair on the nitrogen atom with an electrophile having a silicon based anchor group. Such reactions and precursors are easily selected by the skilled artisan with the teaching herein.
Alkylating electrophiles include, for example, butyl chloride, ethyl chloride, hexyl chloride, and methyl triflate.
Neutral nitrogen containing compounds which have silicon based anchor groups include, for example, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.
Neutral nitrogen containing compounds having a lone electron pair on the nitrogen include, for example, imidazoles, pyrazoles, thiazoles, isothiazoles, azathiozoles, oxothiazoles, oxazines, oxazolines, oxazoboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, boroles, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isooxazoles, isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholenes, pyrans, annolines, phthalzines, quinazolines, quinoxalines, quinolines, isoquinolines, thazines, oxazines, and azaannulenes. In addition acyclic organic systems are also suitable. Examples include, but are not limited to amines (including amidines, imines, guanidines), phosphines (including phosphinimines), arsines, stibines, ethers, thioethers, selenoethers and mixtures of the above.
Electrophiles having a silicon based anchor group include for example, 3-triethoxysilylpropyl-1-chloride.
The precursors for Bxe2x88x92 include for example, salts, alkylates and halogenated salts of the Group Ib, IIIb, IVb, Vb, VIb, and VIIb elements of the periodic table including borates, phosphates, nitrates, sulfates, triflates, halogenated aluminates, halogenated copperates, antimonates, galleates, alkylates aluminates, phosphates, phosphites, substituted and unsubstitted carboranes, poly-oxo metallates, substitutes (fluorinated, alkylated, and arylated) and unsubstituted metalloboranes, substituted and unsubstituted carboxylates and triflates and mixtures thereof. Bxe2x88x92 may also be a non-coordinating anion such as tetra[pentafluoro phenyl]borane. Examples of some of the above include Al2Cl7xe2x88x92, Clxe2x88x92, BF4xe2x88x92, PF6xe2x88x92, AlCl4xe2x88x92, or a metal organic anion.
Thus, in the final composition A+Bxe2x88x92, Bxe2x88x92 will be, for example BF4xe2x88x92, PF6xe2x88x92, NO3xe2x88x92, Clxe2x88x92, halogenxe2x88x92, CF3SO3xe2x88x92, CF3COOxe2x88x92, AlX4xe2x88x92 (where X is halogen), GaX4xe2x88x92 (where X is halogen), Al(R)tX4-t where R is alkyl of 1-12 carbon atoms where t is 0-4, SbF6xe2x88x92, [CuCl2]xe2x88x92, AsF6xe2x88x92, SO4xe2x88x92, CF3CH2CH2COOxe2x88x92, (CF3SO2)3Cxe2x88x92, CF3(CF2)3SO3xe2x88x92, [CF3SO2]2Nxe2x88x92. Preferably Bxe2x88x92 will be selected from Clxe2x88x92, CF3SO3xe2x88x92, CF3COOxe2x88x92, BF4xe2x88x92, PF6xe2x88x92, CF3(CF2)3SO3xe2x88x92, and [CF3SO2]2Nxe2x88x92.
A+ will preferably be selected from: 
Most preferably A will be selected from 
In the formulae depicted earlier for A, p=an integer from 1-4, preferably 1 or 2, r is an integer from 0 to 10, preferably 1 or 2, 1, 1xe2x80x2, and 1xe2x80x3 are integers from 0 to 4, preferably 1, and each of 1, 1xe2x80x2, and 1xe2x80x3 can be different.
For example, to prepare the composition A+Bxe2x88x92 shown below 
The skilled artisan could react 
The Clxe2x88x92 could then be ion exchanged with NaPF6 if desired, yielding A+Bxe2x88x92 with B as either Cl or PF6. This is an example of reacting a neutral nitrogen containing compound with a lone electron pair on the nitrogen with an electrophile having a silicon based anchor group where the silicon based anchor group is Si-alkoxy.
Alternatively, the skilled artisan could react an alkylating electrophile such as butyl chloride with a neutral nitrogen containing compound having a silicon based anchor group as shown below. 
The chloride complex can then be exchanged with NaPF6 in the presence of acetonitrile to replace the Clxe2x88x92 with PF6xe2x88x92 if desired. Prior to exchanging the chloride anion, the compound is preferably evaporated to remove excess butyl chloride. Such a work up procedure is common to the skilled artisan. Further, the compound may then be washed with a non-polar organic solvent such as pentane and dried. The butyl chloride above is referred to as the alkylating agent and the silicon containing ethoxy group as the anchoring group herein which allows the composition A+Bxe2x88x92 to be covalently bonded through A to a support. Alkylating groups other than butyl groups can be introduced accordingly. Refluxing is typically carried out at temperatures up to about 200xc2x0 C., preferably about 55 to about 200, more preferably 55 to 140, even more preferably about 60 to 100 and most preferably about 70 to 90xc2x0 C. Although the reaction can be run at temperatures of up to 200xc2x0 C., it is preferable not to exceed 140xc2x0 C. since degradation will take place and yields will be lower.
In order to provide reaction temperatures which do not exceed 140xc2x0 C., a solvent can be used. For example, 1,1,1-trichloroethane provides lower boiling (xe2x88x92100xc2x0 C.) for the introduction of hexyl or octyl chloride in the alkylation process.
In the above formula for A+Bxe2x88x92
Bxe2x88x92=Clxe2x88x92 or PF6xe2x88x92 if ion exchange with PF6xe2x88x92 has been conducted and A is 
where Rxe2x80x2=CH2CH2CH2 and the other R is butyl and r and p both=1 and where the ring system 
contains two nitrogen and is a five member ring.
Y=(OEt) and
m=0 and n=3.
The supports utilizable in the invention include both organic and inorganic supports including inorganic oxides and polymers. The supports may be selected from, for example, zeolites, clays, silica, alumina, silica-alumina or any other inorganic oxides having hydroxyl or surface oxygen groups.
By surface oxygen groups is meant an oxygen group bound to the surface of the support which can be reacted with the compound A+Bxe2x88x92, of the above formula and thereby covalently bond through the cation of said A+Bxe2x88x92.
The polymeric supports will preferably have the capability to bond to the composition A+Bxe2x88x92 described above through the cation via a Carbon-Carbon bond using a hydrosilylation reaction.
When it is desired to covalently bond the composition A+Bxe2x88x92, to a support, the skilled artisan may conduct a condensation reaction, a ring opening reaction or a hydrosilylation reaction. The skilled artisan will readily know which reaction to conduct depending on the composition A+Bxe2x88x92 and the support selected. For example, for the support depicted below, the skilled artisan would readily recognize that a ring opening reaction would be conducted to covalently bond the support to the compound A+Bxe2x88x92. In the example depicted below, only the SiZ portion of A+ is shown where Z is an ethoxy group (Hence Y=OEt, n=3, m=0). In the ring opening reaction, the surface oxygen present bonds covalently 
to the Si group of A while the OEt group bonds to the Si on the surface of the support. Such a reaction can be carried out in a solution of, for example heptane or toluene and a temperature of about 60 to about 150, preferably about 60 to about 100xc2x0 C., and most preferably about 80xc2x0 C. to form the surface bound species.
It is preferred to heat the support under vacuum at elevated temperatures of about 60 to about 600, preferably about 60 to about 400xc2x0 C., and most preferably about 300xc2x0 C. before surface immobilization (or covalent bonding) of A+Bxe2x88x92 thereto. Heating removes adsorbed water and or volatile hydrolyzable species.
In a further reaction, a second and third ethoxy group can react with the support, either through a condensation reaction, or another ring opening reaction. In the most common case, the silicon atom of A is covalently attached to the surface of the support through 2 Si(of A)xe2x80x94Oxe2x80x94Si(of support) bonds with the third ethoxy group on the silicon atom remaining unreacted. For example: 
An example of a condensation reaction to covalently bond A+Bxe2x88x92 to a support is 
The above reaction is conducted at about 60 to about 200, preferably about 60 to about 100xc2x0 C., and most preferably about 80xc2x0 C.
An example of bonding A+Bxe2x88x92 to a polymeric support is: 
It is understood that in the above examples of bonding of A+Bxe2x88x92 to the various supports that the reaction between only one molecule is being depicted. The above hydrosilylation reaction is conducted with the well-known Karstedt catalyst. For example H2PtCl6.6H2O can be used. One skilled in the art will readily recognize that in view of the chemistry occurring to covalently bond the compound A+Bxe2x88x92 to a support, A+Bxe2x88x92 may not exist as such, but will exist as the compound of the result of the covalent bonding. Clearly, the skilled artisan recognizes that, if a condensation reaction occurs, water, alcohol, HX, etc., will be lost from the joining of the support to the compound A+Bxe2x88x92.
In a ring opening reaction, the compound A+Bxe2x88x92 merely adds to the support across the surface and nothing is lost. In a hydrosilylation reaction, the double bond merely becomes hydrogenated and no leaving groups are present. A carbon-carbon bond is formed.
Following the covalent bonding of A+Bxe2x88x92 to the desired support, an additional ionic liquid may be added to the supported composition. To achieve this, the skilled artisan needs merely to dissolve the ionic liquid of choice in a solvent and mix it with the supported composition. The solvent is then evaporated off. While the solvent is evaporated, the non-volatile ionic liquid concentrates within A+Bxe2x88x92 and is colombically attached thereto. The skilled artisan can readily determine which solvents to utilize by evaluating their compatibility with the supported composition and the ionic liquid. For example [bmin][BF4] where bmin is 3-butyl-1-methylimidizolium readily dissolves in acetonitrile. Evaporation will likewise be conducted at conditions that will not decompose the final composition. For example, air drying or controlled heating may be utilized or evaporation under reduced pressure. The additional ionic liquid referred to herein can be any ionic liquid known to the skilled artisan or alternatively may also be an additional amount of a modified ionic liquid A+Bxe2x88x92 described herein.
The ionic liquids which can be utilized and which may form a part of the compositions described herein, which are immobilized within the composition A+Bxe2x88x92 are any ionic liquid known in the art and mixtures thereof. Examples include those described in P. Bouhote, et al. Inorg. Chem. 1996, 35, 1168-1178 and R. Hagiwara, J. Fluorine Chem. 2000, 105, 221-227.
Following the addition of the ionic liquid, or simultaneous therewith, a catalytically active material can be added to the composition. The catalytic material will associate with the composition through coulombic interaction and will be present within and incorporated within the ionic liquid. The catalyst present may be present as a precursor which is then converted to active catalyst in situ in the process in which the composition is used. The catalyst or precursor utilized herein can be a homogeneous, heterogeneous or biocatalyst or catalyst precursor.
Typically, up to 100 wt % of ionic liquid based on the weight of the supported A+Bxe2x88x92 may be immobilized and coulombically attached to said A+Bxe2x88x92, preferably about 50 wt % to about 10 wt %, more preferably about 25 wt % to about 1 wt % ionic liquid will be present in the composition. When a catalytic material, such as a catalyst or catalyst precursor is also present in the composition, it will be present in amounts of up to the solubility limit of the catalyst in the ionic liquid. Typically about 0.01 to about 1 wt % based on the weight of the composition will be present.
It is also possible for the ionic liquid colombically attached to the supported A+Bxe2x88x92 to act as a catalyst such as for immobilized chloroaluminate ionic liquid phase [bmin][Al2Cl7] which can be a highly acidic catalytic medium.
The compositions of the formula A+Bxe2x88x92 when covalently bonded to a support material are preferably present as a monolayer. As used herein a monolayer may include a partial monolayer. It is sufficient that any amount of A+Bxe2x88x92 be covalently bonded to the surface of the support. However, preferably at least about 50% of the surface of the support will have a monolayer thereon and most preferably at least about 90%.
The following examples are meant to be illustrative and are not meant to be limiting.